This is a 371 national stage application of PCT/EP99/06809, filed on Sep. 14, 1999, which has benefit of European Patent Application 98117342.0, filed on Sep. 14, 1998.
1. Field of the Invention
The invention relates to a surface-modified filler composition, its use for fireproof finishing of thermoplastic, duroplastic or elastomeric plastics, and the fireproof plastics produced therefrom.
2. Background Art
Flame-retardant fillers, such as, e.g., magnesium hydroxide or aluminum hydroxide, are often surface-modified for the purpose of improving the characteristics profile of the plastic mixtures that are produced with these fillers. This could be done with, e.g., salts of fatty acids according to DE-A-26 59 933, with polymers containing acid groups according to EP-A-292 233, with ethylene-propylene-copolymers EPDM or ethylene-propylene-terpolymers and other additives according to EP-B-0 426 196 or with special fatty acid derivatives according to WO-A-96/26240.
A drawback of the coatings of the prior art is the lack of universality. Thus, e.g., in coatings according to WO-A-96/26240, the effect with respect to the improvement of mechanical properties and/or the burning properties is very clearly pronounced in some plastics, such as, e.g., in EVA, but virtually does not occur in other systems, such as, e.g., in aliphatic polyketones, either only conditionally or in plastics such as, e.g., polyamides.
The object was consequently to develop surface-modified filler compositions that do not contain the drawbacks of the prior art, and thus can be used universally in the case of improved polymer compatibility and show improved mechanical and rheological properties and/or improved burning properties in comparison to the uncoated filler. In particular, the object was to develop surface-modified filler compositions that are especially suitable for the production of compounds for cable insulation.
The object can be achieved with the surface-modified filler compositions according to the invention.
According to the invention, the surface-modification of the halogen-free flame-retardant filler consists of one or more organotitanates and/or organozirconates and a siloxane derivative.
As halogen-free flame-retardant fillers, hydroxides of aluminum and/or hydroxides of magnesium, optionally mixed with oxides of aluminum, magnesium, titanium, silicon or zirconium or with other filler materials, such as, e.g, calcium carbonate, talc or calcined or non-calcined clays, are used.
Suitable hydroxides of aluminum are, e.g., natural Al(OH)3-containing materials, such as, e.g., hydrargillite or gibbsite, (AlO(OH)x)-containing materials, such as, e.g., boehmite or synthetic aluminum hydroxides, as they are marketed, e.g., under the trademark MARTIFIN(copyright) or MARTINAL(copyright) of the Alusuisse Martinswerk GmbH in Bergheim (Germany).
Suitable hydroxides of the magnesium are, e.g., natural Mg(OH)2 types, such as, e.g., the brucite or sea water types, natural magnesium hydroxycarbonates, such as, e.g., dawsonite, huntite or hydromagnesite, or synthetic magnesium hydroxides, as are marketed, e.g., under the trademarks MAGNIFIN(copyright) of the Magnifin GmbH in Breitenau (Austria). As oxides of aluminum, magnesium, titanium or zirconium, the commercial oxides can be used. Depending on the required characteristics profile in the plastic, a hydroxide of aluminum and/or a hydroxide of magnesium by itself or in any mixture ratio is used with the above-mentioned oxides.
According to an embodiment of the invention, the filler composition in addition can contain a melamine derivative and/or a guanamine derivative. These additives can contribute to a further improvement of the flameproofing.
Suitable derivatives of the melamine are, e.g., melamine cyanurate/melaminisocyanurate or melaminediborate. A suitable derivative of guanamine is, e.g., acetoguanamine cyanurate.
For the purpose of better application, the melamine derivative and/or guanamine derivative can be taken up in a suitable vehicle. Such vehicles can be selected from polymers whose melting points are as much as possible below 150xc2x0 C., from a suitable highly volatile organic solvent, which can be removed in further processing by evaporation, or from the organotitanates and/or organozirconates and a siloxane derivative that are used according to the invention.
The melamine derivative and/or guanamine derivative is suitably used in an amount of 0.01 to 25 parts, preferably 0.5 to 15 parts per 100 parts of halogen-free flame-retardant filler.
Suitable organotitanates and/or organozirconates are, e.g., those as described in the company publication xe2x80x9cKen-React Reference Manual,xe2x80x9d Bulletin KR-1084-2 of the Kenrich Petrochemicals Inc; or as the are marketed by, e.g., the DuPont Company under the trade name TYZOR(copyright).
Suitable organotitaniums or oragnozirconates are, for example:
Titanium tetra-2-ethylhexanoate, titanium tetrabutanolate, tetraisopropyl titanate, triethanolamine zirconate, tetra-n-propyl-zirconate, tetra-n-butyl-zirconate, diethylcitrate chelate-zirconate,
(triisosteary-isopropyl-titanate), tris-isooctadecanoato-O-titanium(IV)-2-propanolate,
iscoctadecancato-O-2-propanolato-titanium(IV) bis-2-methyl-2-propanolate,
tris(dodecyl)benzosulfonato-O-titanium(IV) 2-propanolate,
tris(dioctyl)phosphato-O-titanium(IV) 2-propanolate,
bis(dodecyl)benzosulfonato-O-2-propanolato-titanium(IV) (4-amino)benzenesulfonate,
methoxydiglycolato-O-titanium(IV) tris(2-methyl)-2-propenoate,
tris(dioctyl)pyrophosphato-O-titanium(IV) 2-propanolate,
methoxydiglycolato-O-titanium(IV) tris(2-propenoate),
tris(3,6-diaza)hexanolato-titanium(IV)-2-propanolate,
oxoethylenediolato-titanium(IV) bis[4-(2-phenyl)-2-propyl-2]phenolate,
titanium(IV) bis(dioctyl)pyrophosphato-O-oxcethylenediolate, adduct with (dioctyl-O-hydrogenphosphite),
tris-(2-methyl)-2-propenoato-O-titanium(IV) oxoethylenediolate,
titanium(IV) bis(butyl,methyl)pyrophosphato-O-oxoethylene-diolate, adduct with bis(dioctyl)-hydrogenphosphite,
ethylenediolato-O-titanium(IV) bis (dioctyl)phosphate,
ethylenediolato-O-titanium(IV) bis (dioctyl)pyrophosphate, adduct with bis(dioctyl)-hydrogenphosphite,
ethylenediolato-O-titanium(IV) bis(butyl,methyl)pyrophosphate, adduct with bis(dioctyl)-hydrogenphosphite,
oxoethylenediolato-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of 2-N,N-dimethylamino-2-methylpropanol,
methylpyrophosphato-O-titanium(IV) bis(butyl), adduct with 2 mol of 2-N,N-dimethylamino-2-methylpropanol, bis(dioctyl)pyrophosphato-O-titanium(IV) ethylenediolate-bis-(triethyl)amine salt,
bis(dioctyl)pyrophosphato-O-bis(dialkyl)aminoalkyl-2-methylpropenoate-titanium(IV) ethylenediolate,
ethylenediolato-O-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of acrylato-O-amine,
ethylenediolato-O-titanium(IV) bis(dioctyl)pyrophosphate, adduct with 2 mol of 2-methylpropenoamido-N-amine,
methylpyrophosphato-ethylenediolato-titanium(IV) bis(butyl)-bis(dialkyl)aminoalkylacrylate salt,
bis(dioctyl)pyrophosphato-O-titanium(IV) (bis-2-propenolatemethyl)-2-butanolate, adduct with 3 mol of N,N-dimethylaminoalkylpropenoamide,
bis(dioctyl)pyrophosphato-O-zirconium(IV) 2,2-dimethyl-1,3-propanediolate, adduct with 2 mol of N,N-dimethylaminoalkylpropenoamide,
cyclo-bis-2-dimethylaminopyrophosphato-O,O-zirconium(IV) (2-ethyl, 2-propenolatomethyl)1,3-propanediolate, adduct with 2 mol of methanesulfonic acid,
titanium(IV) tetrakis-2-propanolate, adduct with 2 mol of (dioctyl)hydrogen phosphate,
titanium(IV) tetrakis octanolate, adduct with 2 mol of (ditridecyl)hydrogen phosphite,
methylbutanolato-titanium(IV) tetrakis(bis-2-propenolate), adduct with 2 mol of (di-tridecyl)-hydrogen phosphite,
zirconium(IV) tetrakis-2,2-(bis-2-propenolatomethyl)butanolate, adduct with 2 mol of ditridecyl hydrogen phosphite,
tris-neodecanolato-O-titanium(IV) 2,2-(bis-3-propenolatomethyl)butanolate,
tris(dodecyl)benzenesulfonato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)phosphato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)pyrophosphato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(2-ethylenediamino ethylato-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(3-amino)-phenylato-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(6-hydroxy)hexanoato-O-titanium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
cyclo(dioctyl)pyrophosphato-O,O-titanium(IV) bis-octanolate,
titanium(IV) bis-cyclo(dioctyl)pyrophosphate,
cyclo-di-2,2-(bis-2-propenolatomethyl) butanolatopyrophosphato-O,O-zirconium(IV) 2-ethyl,2-propenolatomethyl-1,3-propanediolate,
cyclo(di-2-ethylhexyl)pyrophosphato-zirconium(IV) to 2-ethylhexanolate,
tris-neodecanolato-O-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dodecyl)benzenesulfonato-O-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)phosphato-O-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate, tris-2-methyl-2-propenolato-O-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris(dioctyl)pyrophosphato-O-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
tris-2-propenolato-O-zirconium(IV) 2,2-(bis-2-propenolato)butanolate,
tris(2-ethylenediamino)ethylato-zirconium(IV) 2,2-(bis-2-propenolatomethyl)butanolate,
bis-(9,10-11,12-diepoxy)octadecanoato-O-zirconium(IV) bis-(2,2-dimethyl-1,3-propanediolate, zirconium(IV) 2-ethyl-2-propenolatomethyl-1,3-propanediolate-bis-mercaptophenylate,
tris(2-amino)phenylato-zirconium(IV) 1,1-(bis-2-propenolatomethyl)butanolate.
These compounds can be used individually or as a mixture.
Preferred organotitanates and/or organozirconates are, e.g., titanium tetra-2-ethylhexanoate, tris-isooctadecanoato-O-titanium(IV)-2-propanolate, (triisostearyl isopropyl titanate), titanium tetrabutanolate and tetraisopropyl titanate, triethanolamine zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate and diethylcitrate chelate-zirconate.
The organotitanates and/or organozirconates are suitably used in an amount of 0.01 to 10 parts, preferably 0.1 to 5 parts per 100 parts of halogen-free flame-retardant filler.
For the purpose of optimizing the mechanical properties, such as, e.g., the tensile strength, the elongation at break, and the modulus of elasticity, the organotitanate and/or the organozirconate can be used in combination with a suitable silane.
Suitably those silanes are used as they are described in, e.g., DE-A-27 43 682 or are indicated from the company prospectus of Hxc3xcls AG Marl, xe2x80x9cLieferprogramme Silane-Kieselsxc3xa4ureester-Metallsxc3xa4ureester, -chelate [Delivery Programs of Silane-silicic Acid Ester-Metal Acid Esters, -Chelates],xe2x80x9d February 1994. Vinylsilanes, such as, e.g., vinyltriethoxysilane or vinyltrimethoxysilane, aminosilanes, such as, e.g., N-methyl-3-aminopropyl-trimethoxysilane, methacrylic silanes, such as, e.g., (methacryloyloxypropyl)-trimethoxysilanes, epoxysilanes, such as, e.g., 3-glycidyloxypropyl-trimethoxysilane, or alkylsilanes, such as, e.g., propyltriethoxysilane, are preferably used.
A mixture of the above-mentioned silanes can optionally also be used.
The silane is usually used in an amount of 0.01 to 10 parts, preferably 0.5 to 5 parts per 100 parts of-halogen-free flame-retardant filler.
According to the invention, the halogen-free, flame-retardant filler is treated in addition with a siloxane derivative. A polysiloxane is suitably used as a siloxane derivative. Suitable polysiloxanes are the oligoalkylsiloxanes, the polydialkylsiloxanes, such as, e.g., the polydimethylsiloxane or polydiethylsiloxane, the polyalkylarylsiloxanes, such as, e.g., the polyphenylmethylsiloxane, or the polydiarylsiloxanes, such as, e.g., the polyphenylsiloxane. The above-mentioned siloxanes can be functionalized with reactive groups, such as, e.g., hydroxy, amino, vinyl, acryl, methacryl, carboxy or glycidyl.
High-molecular polydialkylsiloxanes, which optionally are modified with the above-mentioned functional groups, are preferably used.
Mixtures of the above-mentioned siloxane derivatives optionally can be used. The siloxane derivative is generally used in an amount of 0.01 to 20 parts, preferably 0.05 to 10 parts per 100 parts of halogen-free flame-retardant filler.
For surface-modification, the halogen-free, flame-retardant filler suitably in a suitable mixer, preferably in a mixer that makes possible high shearing forces, is provided with the above-mentioned co-agents. In this case, the addition times or intervals and the process temperatures can be adapted to the reactivity of the co-agents with the filler surface. It is also possible to feed to the mixer a premixture of the co-agents together with the halogen-free flame-retardant filler.
Advantageously, an additive concentrate, a so-called master batch, can also first be produced by only a partial amount of the filler being mixed with the co-agents in question according to the above-mentioned process in a mixer with high shearing forces. This so-called master batch can then be diluted in a simple way with a technically less expensive mixing device, e.g., at the customer""s site, with the corresponding amount of additional filler, and can be processed into ready-to-use surface-modified filler.
The halogen-free, flame-retardant filler that is modified in this way can then be processed into a compound with the desired polymer according to standard methods. Compounding devices include commercial mixing devices, such as, e.g., single- or twin-screw kneaders, co-kneaders, closed mixers or an FCM (farrel continuous mixer).
The surface-treated, halogen-free, flame-retardant filler according to the invention is suitable for the fireproof finishing of thermoplasts, duroplasts or elastomers. From the series of thermoplasts, e.g., polyethylene and its copolymers, polypropylene, EVA and its copolymers, EEA and its copolymers, polyamide and its copolymers, aliphatic polyketones or polyesters are suitable. As elastomers, e.g., rubbers such as EPM, EPDM, SBR, chloroprene rubber and nitrile rubber are considered.
The content of surface-treated filler in the polymer matrix in question shifts depending on the desired degree of flame-retardancy, generally between 5 and 90% by weight, preferably between 20 to 70% by weight relative to the filled polymer.
The surface-treated, halogen-free flame-retardant fillers in the above-mentioned thermoplasts, especially in EVA, EEA, PE, PP, PA and aliphatic polyketones, are preferably used.
Depending on the required characteristics profile, the above-mentioned fillers can be mixed into one or more oxides of aluminum, magnesium, titanium, silicon or zirconium to control, e.g., abrasion behavior, hardness or weathering properties.
The above-mentioned filler-containing compounds can contain additional fiber-like reinforcing substances. The fiber substances include, for example, glass fibers, stone fibers, metal fibers, polycrystalline ceramic fibers, including monocrystals, so-called xe2x80x9cwhiskers,xe2x80x9d also all fibers that originate from synthetic polymers, such as, e.g., aramide, carbon, polyamide, polyacryl, polyester and polyethylene fibers.
If desired, the compounds can be provided with suitable pigments and/or dyes or with other application-specific additives or adjuvants.